Materials which can provide patchouli-like and woody fragrance notes are known in the art of perfumery. Many of the natural materials which provide such fragrances and contribute desired nuances to perfumery compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
There is accordingly a continuing effort to find synthetic materials which will replace the essential fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the compositions. The search for materials which can provide a more refined patchouli-like fragrance has been difficult and relatively costly in the areas of both natural products and synthetic products.
Buchi et al., 83 J. Am. Chem. Soc. 927 (1961), shows the production of a material called "patchoulione" which is stated to be octahydro-1,4,9,9-tetramethyl-3a, 7-methanoazulen-5(4H)-one having the structure: ##STR1##
U.S. Pat. No. 3,748,284 issued on July 24, 1973 discloses perhydro derivatives of methanoazulene as having camphoraceous woody fragrances and having the ability to impart this fragrance to perfumed compositions and perfumed articles. The compounds disclosed are:
(A) Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-3 (2H)-one having the structure: ##SPC4##
(B) Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-2 (3H)-one having the structure: ##SPC5## ; and
(C) Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-8 (7H)-one having the structure: ##SPC6##
Umarani et al., Sept./Oct. 1969, P. & E.O.R., 307 discloses two compounds relevant to the instant case: "isopatchoulinol" having the structure: ##SPC7##
and "patchouli alcohol" having the structure: ##SPC8##
Mirrington and Schmalzl 37 J. Org. Chem. No. 18, 1972, pages 2871-2877 discloses the isolation of (-) patchouli alcohol having the structure: ##SPC9##
An article by Corey and Wipke entitled "Computer-Assisted Design of Complex Organic Syntheses" appearing in 166 Science 178 (1969) sets forth, interalia, the sequence of reactions leading to compounds having the structures: ##SPC10##
One of these reaction sequences involves performing the reactions: ##SPC11## ##SPC12##
However, syntheses of methyl homologues and double compound isomers and an analogues patchouli alcohol and dihydropatchouli alcohol have not yet been disclosed in the prior art. Indeed, economic syntheses of patchouli alcohol itself do not appear to be given in the literature.
Danishevsky and Dumas 1968 Chemical Communication, Pages 1287-1288 discloses the synthesis of racemic patchouli alcohol and epi patchouli alcohol having the structure: ##SPC13##
by means of cyclization of a compound having the structure: ##SPC14##
The use in perfumery of the compound having the structure: ##SPC15##
("norpatchoulinol") is disclosed in the following publications:
1. Belgian Patent No. 788,301 issued Mar. 1, 1973 PA1 2. German Offenlegungschrift 2,242,913 published Mar. 8, 1973 PA1 3. Dutch published Application 72/11760 published Mar. 5, 1973 PA1 a. First intimately admixing 2,6,6-trimethyl-cyclohexadien-1-one having the structure: ##SPC30##
A product of the reduction of this compound is also disclosed ("dihydro norpatchoulinol"). This product has the structure: ##SPC16##
It is also disclosed in application for U.S. Pat. No. 436,846 filed on Jan. 28, 1974 that as a result of analyzing natural patchouli oil, it was found that cis-2-n-pentylcyclopropane-1-carboxylic acid having the structure: ##SPC17##
is a key component for patchouli fragrance having a patchouli-like animal, leathery note and having the capability of imparting such notes to perfumes and cosmetic compositions.
Tetracyclic terpenes having structures and properties different in kind from the compounds of our invention have been previously examined and synthesized, for example, "ishwarane" and "ishwarone" having the structures: ##SPC18##
wherein Z=H, H or Z=O
as well as another tetracyclic ketone having the structure: ##SPC19##
(Kelly et al., Can. J. Chem. 50 (21) 3455-65, 1972) and "myliol" having the structure: ##SPC20##
obtained from liverwort M. Taylorii (Benesova et al., Collect. Czech. Chem. Commun. 38 (4) 1084-90, 1973), Benesova et al. also discloses a compound having the structure: ##SPC21##
The compounds of our invention have properties considered to be unobvious, unexpected and advantageous with respect to the properties of the above mentioned prior art compounds.